CN101675126B - Antifouling coating composition based on curable polyorganosiloxane polyoxyalkylene copolymers - Google Patents

Antifouling coating composition based on curable polyorganosiloxane polyoxyalkylene copolymers Download PDF

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CN101675126B
CN101675126B CN200880014177.XA CN200880014177A CN101675126B CN 101675126 B CN101675126 B CN 101675126B CN 200880014177 A CN200880014177 A CN 200880014177A CN 101675126 B CN101675126 B CN 101675126B
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active group
linking agent
segmented copolymer
coating composition
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CN101675126A (en
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D·N·威廉姆斯
D·A·斯塔克
A·J·李
C·M·戴维斯
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Akzo Nobel Coatings International BV
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1656—Antifouling paints; Underwater paints characterised by the film-forming substance
    • C09D5/1662—Synthetic film-forming substance
    • C09D5/1675—Polyorganosiloxane-containing compositions
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/02—Polysilicates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
    • C09D183/10—Block or graft copolymers containing polysiloxane sequences
    • C09D183/12—Block or graft copolymers containing polysiloxane sequences containing polyether sequences
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)
  • Silicon Polymers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

A process to physically deter fouling from a substrate in an aquatic fouling environment, which process comprises forming on the substrate, before exposure to the said environment, a coating composition comprising (i) a curable polyorganosiloxane polyoxyalkylene block copolymer having at least two reactive groups X situated on the copolymer chain and (ii) an organosilicon crosslinking agent and/or a catalyst.

Description

Based on the antifouling paint compositions of curable polyorganosiloxane polyoxyalkylene copolymers
The present invention relates to use the coating composition containing organopolysiloxane to prevent substrate contaminated method and the substrate that scribbles described coating composition in aquatic environment with physics mode.
Water-immersed man-made structures is easy to be subject to aquatic organism as the pollution of green alga and brown alga, barnacle and mussel etc. as hull, buoy, production platform, graving dry dock equipment, oil recovery boring tower and pipeline.This class formation is generally metal, but also can contain other structured material as concrete.This pollution has detrimental effect to hull, because it has increased the friction resistance during moving in water, result increases Speed Reduction and fuel cost.It has detrimental effect to static structure body as the support of production platform and oil recovery boring tower, first because thick pollution layer may cause the unpredictable and proemial stress of tool to the resistance of wave and current in this structure, secondly make the defect that is difficult to check this structure as stress cracking and corrosion because pollute.It has detrimental effect to pipeline as cooling water inlet and outlet, because pollute, to have reduced effective cross section long-pending, and result flow velocity reduces.
The successful methods that commercial inhibition is polluted relates to using and contains the poisonous material of hydrobiont as the antifouling coating of tributyltin chloride or Red copper oxide.But if may have destruction because this toxoid is discharged in aquatic environment, people more and more do not support this type coating.Correspondingly, need the uncontamination coating of not obvious release toxic substance.
For many years, known for example as GB 1,307,001 and US 3,702,778 in disclosed, silicone rubber coating can be resisted aquatic organism and pollute.It is believed that this type coating provides body and be not easy to adhere to its surface, correspondingly can be referred to as to pollute and discharge (fouling release) coating but not antifouling coating.Silicon rubber and polysiloxane compound have low-down toxicity conventionally.In the time being applied to hull, although the shortcoming of described anti-fouling system is to have reduced, extra large life is organic gathers, and removes the relatively high ship's speed of all contaminants kind needs.Therefore, in some cases, be indicated as from effectively discharging with the hull that this type of polymer treatment is crossed, need to be with the speed navigation of at least 14 joints.For this reason, silicon rubber has obtained limited business success, need to improve the antifouling of these environmentally friendly coatings and pollute release performance.
US 6,906,161 discloses the antifouling paint compositions of room-temperature-curable, and described composition is included in the formula-R that has at least one in each molecule and be bonded to Siliciumatom 2-Si (R 3) 2-O-(R 4o) b-R 5the organopolysiloxane of side group.In the formula, the integer that b is 1-30, R 2and R 3for the alkyl of 1-6 carbon atom, R 4for the alkylidene group of 2-4 carbon atom, R 5for the alkyl of 1-8 carbon atom or by-R 6-SiX 3the group of representative, wherein R 6for the alkyl of 1-6 carbon atom, X is hydrolyzable group.
WO 2004/081121 discloses a kind of antifouling paint compositions, and described composition comprises the multipolymer that obtains and contain divalent metal atom containing the monomer mixture polymerization of Si monomer that has two (methyl) acryl end groups by making to comprise.
Even if having now found that the coating composition that comprises specific copolymer by use also can further reduce the raw physics polluting in sea and hinder under static conditions.
Therefore, the present invention relates to prevent substrate contaminated method in aquatic contaminate environment with physics mode, described method is included in to be exposed to and on substrate, forms coating composition before described environment, and described coating composition comprises (i) to be had at least two and be positioned at the curable polyorganosiloxane polyoxyalkylene segmented copolymer of the active group X on polymer chain and (ii) organosilicon cross-linking agent and/or catalyzer.
If described radicals X is not reacted each other, coating composition comprises the organosilicon cross-linking agent with at least two group Y that react with described radicals X.In addition, it also can comprise catalyzer and is cross-linked promoting.If the each molecule of polyorganosiloxane polyoxyalkylene copolymers only has two nonreactive active group X each other, coating composition comprises each molecule and on average has the organosilicon cross-linking agent of plural active group Y.If described radicals X can be reacted each other, coating composition comprises catalyzer and is cross-linked promoting.In addition, its also can comprise have at least two with the organosilicon cross-linking agent of the good group Y answering of described radicals X.
Multipolymer does not need to exist divalent metal as Mg, Zn or Cu.Therefore, in preferred embodiments, multipolymer does not contain this metalloid.Described coating composition is applied on substrate and solidifies to form coated substrate.Gained coating is made up of the water-fast hydrophilic polymer network that comprises the organosilicon crosslinked part polyorganosiloxane polyoxyalkylene segmented copolymer connected to one another chain of being combined by the key between the crosslink sites on polyorganosiloxane polyoxyalkylene segmented copolymer chain and/or by the crosslink sites on polyorganosiloxane polyoxyalkylene segmented copolymer chain.In preferred embodiments, polyorganosiloxane polyoxyalkylene segmented copolymer interchain is crosslinked in fact not containing Si-O-C key.
Polyorganosiloxane polyoxyalkylene segmented copolymer
In this specification sheets, segmented copolymer is defined as to the basic multipolymer for straight chain with the chain being formed by the homopolymer block linking together.These blocks can connect by any way, for example alternately or random.Preferably, the organopolysiloxane block being present in segmented copolymer contains 5-30 siloxanes alkane unit independently of one another.More preferably, polyoxyalkylene block contains 2-30 oxyalkylene units independently of one another.
The preferred polyorganosiloxane polyoxyalkylene segmented copolymer of the first kind is PS-(A-PO-A-PS) nthe segmented copolymer of the organopolysiloxane end-blocking of form, wherein PS represents organopolysiloxane block, and PO represents polyoxyalkylene block, and A represents divalent moiety, and the value of n is at least 1, is preferably 10-250.Can use other segmented copolymer, for example segmented copolymer of branched block multipolymer, polyoxyalkylene end-blocking or there is organopolysiloxane and the segmented copolymer of polyoxyalkylene terminal block.In preferred embodiments, active group X is positioned on the Siliciumatom of segmented copolymer separately, if but multipolymer is used together with organosilicon cross-linking agent, this is also nonessential.Even more preferably, active group X is arranged in the organopolysiloxane block of multipolymer.Crosslinkable active group X can for example be positioned in the terminal silicon atom of organopolysiloxane block of multipolymer, if particularly multipolymer is PS-(A-PO-A-PS) nform.
In one embodiment, polyorganosiloxane polyoxyalkylene segmented copolymer has PS '-(A-PO-A-PS ') nform, wherein PS ' represents the organopolysiloxane block of the Siliciumatom end-blocking replacing with alkoxyl group of Shi-Si (R ') (R ')-OR, wherein R representative has the alkyl of 1-4 carbon atom, and each R ' representative has the alkoxyl group of alkyl, phenyl or the formula-OR of 1-6 carbon atom.The example of this type of group is trimethoxysilyl, triethoxysilyl, methyl diethoxy silyl, methyl dimethoxy oxygen base silyl, dimethylmethoxysilylgroups groups and dimethyl (ethoxymethyl) silylation.
Form is PS-(A-PO-A-PS) npolyorganosiloxane polyoxyalkylene segmented copolymer can be in hydrosilylation reactions by the organopolysiloxane with two Si-H groups is prepared with respect to the quantitative response of the excessive existence of ethylenically unsaturated group with the polyethers that contains two ethylenically unsaturated groups so that Si-H group.Ethylenically unsaturated group refers to formula > CH=CH 2group.Described reaction is carried out conventionally under hydrosilylation catalysts exists as platinum metals or its compound.Depend on the ethylenically unsaturated group of polyethers, the divalent moiety A that type hydrogenation Silanization reaction produces thus has for example alkylene moiety of 2-6 carbon atom.Can be branching with the organopolysiloxane of polyether reactant, there is 2-250 siloxane unit but be preferably, more preferably 2-100 siloxane unit, most preferably the straight chain polydiorganosiloxane of the polymerization degree of 4-40 siloxane unit (DP).The organic group of organopolysiloxane is preferably selected from phenyl and has 1-18, the preferably alkyl of 1-6 carbon atom.Most preferably, at least 90% the organic group that is connected to Si is methyl; For example, organopolysiloxane is the polydimethylsiloxane with Si-H functional group.Organopolysiloxane can contain plural Si-H group, but this may cause branching polyorganosiloxane polyoxyalkylene copolymers.Most preferably, shown in following text response figure, organopolysiloxane only has two Si-H groups, all there is one in every one end of polydiorganosiloxane chain, thereby make and the segmented copolymer that generates organopolysiloxane end-blocking that reacts of polyethers, wherein active Si-H group is positioned in the terminal silicon atom of organopolysiloxane block of multipolymer.
The block class SPE of SiH end-blocking
Or can use on non-end siloxane unit or there is the organopolysiloxane of Si-H group endways with on non-end siloxane unit.
Wanted hydrophilicity by obtaining, preferably in polyoxyalkylene block, at least 50% polyoxyalkylene unit is oxygen ethylene unit.Therefore, be preferably polyethylene oxide for the preparation of the polyethers of polyorganosiloxane polyoxyalkylene segmented copolymer, but poly-(the oxygen ethylene oxy propylene) multipolymer that also can use polyoxyethylene unit to be in the great majority.The ethylenically unsaturated group of polyethers can be for example allyl group, vinyl, hexenyl or isobutenyl.An example of preferred, polyethers is polyoxyethylene glycol diallyl ether.Polyethylene oxide preferably has 4-100, the more preferably polymerization degree of 4-40 oxygen ethylene unit.
In polyorganosiloxane polyoxyalkylene copolymers, oxyalkylene is preferably 0.05 to the mol ratio of siloxane unit as oxygen ethylene unit: 1-0.5: 1.
There is the organopolysiloxane of Si-H functional group and the polyethers that contains ethylenically unsaturated group preferably with 1.5: 1-6: 1, more preferably 2: 1-4: 1 Si-H group and the molar ratio reaction of ethylenically unsaturated group.Reaction can be carried out at ambient temperature, but may preferred 60-200 DEG C, for example the rising temperature of 100-150 DEG C.Reaction is conventionally carried out under existing as the catalyzer of platinum or rhodium containing platinum metals.A kind of preferred platinum catalyst is chloroplatinic acid or Platinic chloride and the reaction product that contains the undersaturated silicoorganic compound of end aliphatics; Another kind is platinum divinyl tetramethyl disiloxane title complex.Catalyzer preferably has organopolysiloxane 0.00001-0.5 part of Si-H functional group with every 100 weight parts, most preferably the amount of 0.00001-0.002 part platinum or rhodium is used.Or, can use the polyethers that contains ethylenically unsaturated group of molar excess to make to have the organopolysiloxane of Si-H functional group and the polyether reactant that contains ethylenically unsaturated group, the for example mol ratio of Si-H group and ethylenically unsaturated group is 1: 1.5-1: 6, generate thus PO-(A-PS-A-PO) nthe segmented copolymer of form, wherein as defined above, PO block has end ethylenically unsaturated group for PO, PS and A.This based block copolymer can be cross-linked the water-fast hydrophilic polymer network of generation the present invention as gathered (methyl hydrogen siloxane) or methyl hydrogen siloxane dimethylsiloxane copolymer by the organosilicon cross-linking agent with active Si-H group.Or, can make end ethylenically unsaturated group and suitable silane reaction to be translated into active group X.
Organosilicon cross-linking agent
As mentioned above, if the radicals X being positioned on the organopolysiloxane block of multipolymer is not reacted each other, the organosilicon cross-linking agent that need to have at least two group Y that react with described radicals X for coating composition of the present invention exists.In addition, composition can comprise catalyzer.
If the each molecule of polyorganosiloxane polyoxyalkylene segmented copolymer only has two active group X, composition comprises organosilicon cross-linking agent that each molecule on average has a plural active group Y (for example each molecule 2.5-6 active group) to contribute to network to form (being cross-linked) but not chain extension only.For example, if organosilicon crosslinked group is the branching organopolysiloxane that contains at least three active group Y, it can be combined with at least three polymer chains.
The example of proper group X is Si-H group, Si-alkoxyl group, silanol group, amido, hydroxy-acid group, thiol group, epoxy group(ing), ketoxime base, acetoxyl group and ethylenically unsaturated group.Can be selected from identical sequence with the group Y that one or more these radicals X are reacted, wherein select to depend on the respective reactivity of itself and selected radicals X.
In the time that radicals X is Si-H group
If active group X is Si-H group, organosilicon cross-linking agent can contain ethylenically unsaturated group Y.This type of organosilicon cross-linking agent is preferably polysiloxane.Polysiloxane can be for example by being selected from formula (SiO 4/2) Q unit, formula R csiO 3/2t unit, formula R b 2siO 2/2d unit and formula R a 3siO 1/2the siloxane unit composition of M unit, wherein R a, R band R csubstituting group is selected from alkyl and the thiazolinyl with 1-6 carbon atom, wherein at least three R a, R band/or R csubstituting group is thiazolinyl unit.If polyorganosiloxane polyoxyalkylene segmented copolymer is PS-(A-PO-A-PS) nform, wherein active Si-H radicals X is positioned in the terminal silicon atom of organopolysiloxane block, and a kind of suitable linking agent is the branching organopolysiloxane with the ethylenically unsaturated group Y being positioned at least three side chains.This type of branching organopolysiloxane comprises Q and/or T unit, M unit and optional D unit conventionally.Thiazolinyl is preferably present in M unit.Organopolysiloxane can be for example for containing one or more formula (SiO 4/2) Q unit, a 0-250 formula R b 2siO 2/2d unit and formula R ar b 2siO 1/2the branched silicone of M unit, wherein R aand R bsubstituting group is selected from alkyl and the thiazolinyl with 1-6 carbon atom, wherein at least three R in branched silicone asubstituting group is thiazolinyl unit.If polyorganosiloxane polyoxyalkylene segmented copolymer has longer chain length, the preferred low-molecular-weight Q branched silicone linking agent of possibility, the Q branched silicone with vinyl-functional that for example contains a Q unit, four dimethyl vinyl silyl M unit and 0-20 dimethyl siloxane D unit, it can have following formula structure.
If polyorganosiloxane polyoxyalkylene segmented copolymer contains plural Si-H group, organosilicon cross-linking agent does not need to contain plural ethylenically unsaturated group.For example, linking agent can be and contains two ethylenically unsaturated groups as the polydiorganosiloxane of the polydimethylsiloxane of dimethyl vinyl silyl end-blocking, or its mixture that can be this type of polydiorganosiloxane that contains two ethylenically unsaturated groups and have the branching organopolysiloxane of the ethylenically unsaturated group Y being positioned at least three side chains.
If polyorganosiloxane polyoxyalkylene segmented copolymer contains ethylenically unsaturated group Y containing active group X and the organosilicon cross-linking agent of promising Si-H group, its conventionally contain platinum metals exist as the catalyzer of platinum or rhodium under reaction.Preferred platinum catalyst is described above.Catalyzer preferably has polyorganosiloxane polyoxyalkylene segmented copolymer 0.00001-0.5 part platinum of Si-H functional group with every 100 weight parts or the amount of rhodium is used.The polyorganosiloxane polyoxyalkylene segmented copolymer that contains Si-H group and organosilicon cross-linking agent are preferably with 1.5: 1-6: 1, more preferably 2: 1-4: 1 Si-H group and the molar ratio reaction of ethylenically unsaturated group.Crosslinking reaction can be carried out at ambient temperature, but carries out comparatively fast at the rising temperature of 60-200 DEG C.
Because there is at ambient temperature crosslinking reaction in the time that the polyorganosiloxane polyoxyalkylene segmented copolymer that contains Si-H group, the linking agent that contains ethylenically unsaturated group all contact with catalyzer, therefore can preferably the curable coating composition based on this type of active group be packaged in two containers, thereby make polyorganosiloxane polyoxyalkylene segmented copolymer, linking agent and catalyzer not all in same package.Can be in application not long ago by the contents mixed of these two containers.For example, catalyzer can be packed together with containing the linking agent of ethylenically unsaturated group, the polyorganosiloxane polyoxyalkylene segmented copolymer that contains Si-H group is in independent container.Or, can be by packaging together to polyorganosiloxane polyoxyalkylene segmented copolymer and linking agent, and by optionally packaging separately together with part polyorganosiloxane polyoxyalkylene block copolymer component or partial cross-linked dose of component of catalyzer.
In the time that radicals X is Si-alkoxyl group or silanol group
If active group X is Si-alkoxyl group, it can (i) reaction or the active group Y (ii) and on linking agent (if existed, being Si-alkoxyl group or silanol group) reaction each other under moisture and catalyzer existence.If active group X is silanol group, it can react by the active group Y on the linking agent that is selected from alkoxyl group, acetoxyl group, ketoxime, acid amides or the hydroxyl of being combined with silicon.Therefore coating can contain polyorganosiloxane polyoxyalkylene segmented copolymer chain, and its Si-O-Si key by the Si-alkoxyl group crosslink sites derived from polyorganosiloxane polyoxyalkylene segmented copolymer chain end is connected to each other.
Active group X on polyorganosiloxane polyoxyalkylene segmented copolymer can be for example with formula-Si (R ') 2-OR group exists, and wherein R representative has the alkyl of 1-4 carbon atom, and each R ' representative has the alkoxyl group of alkyl, phenyl or the formula-OR of 1-6 carbon atom.The example of this type of group is trimethoxysilyl, triethoxysilyl, methyl diethoxy silyl, methyl dimethoxy oxygen base silyl, dimethylmethoxysilylgroups groups and dimethyl (ethoxymethyl) silylation.
Active group Y on linking agent also can formula-Si (R ') 2(OR) group exists, and wherein R and R ' have given implication above.In its simplest form, linking agent can be orthosilicic acid tetraalkyl ester, for example original quanmethyl silicate, tetra-ethyl ester, orthocarbonate or four butyl esters, trialkoxy silane, for example alkyltrialkoxysilaneand, for example methyltrimethoxy silane, Union carbide A-162, ethyl triethoxysilane or n-octyl triethoxyl silane, or dialkoxy silicane, for example dialkyl group dimethoxy silane, for example dimethyldimethoxysil,ne, or dialkyl group diethoxy silane, for example dimethyldiethoxysilane.
If polyorganosiloxane polyoxyalkylene segmented copolymer only contains the alkoxyl group of two Si combinations, organosilicon cross-linking agent should contain the alkoxyl group of plural Si combination; For example, its can be trialkoxy silane or contain at least one-Si (OR) 3the polysiloxane (wherein R as defined above) of unit, (R ") (OR) to contain at least two-Si 2the polysiloxane of unit or contain at least three-Si (R ") 2(OR) polysiloxane of unit (wherein R " for thering is the alkyl of 1-6 carbon atom).
If the alkoxyl group that polyorganosiloxane polyoxyalkylene segmented copolymer contains plural Si combination, the organosilicon cross-linking agent of the alkoxyl group that can use the organosilicon cross-linking agent of the alkoxyl group that only contains two Si combinations and/or contain plural Si combination.Or, can be by moisture with preferably under condensation catalyst exists, Si-alkoxyl group is reacted each other to solidify the polyorganosiloxane polyoxyalkylene segmented copolymer of this type of alkoxyl group that contains plural Si combination, and without other linking agent.The polyorganosiloxane polyoxyalkylene segmented copolymer of the alkoxyl group that contains plural Si combination is the self-crosslinkable polymkeric substance of the water-fast hydrophilic polymer network of curable one-tenth.The example of this analog copolymer be use-Si (R ' 2) (OR) 2unit terminated polyorganosiloxane polyoxyalkylene segmented copolymer, wherein R and R ' are as defined above.For example PS-(A-PO-A-PS) nthe segmented copolymer of form, wherein active Si (R ') (OR) 2unit is positioned in the terminal silicon atom of organopolysiloxane block.Or the polyorganosiloxane polyoxyalkylene segmented copolymer of the alkoxyl group that contains Si combination can be PO-(A-PS-A-PO) nthe segmented copolymer of form.This type of segmented copolymer with end ethylenically unsaturated group can be prepared as mentioned above, and can with formula H-Si (R ') 2(OR) silane (wherein R and R ' are as defined above) reacts ethylenically unsaturated group is converted into the formula-Si (R ') that contains 1,2 or 3 active alkoxyl group on the Siliciumatom being connected to separately in polyorganosiloxane polyoxyalkylene segmented copolymer 2(OR) active group.The example of this one type of silane is Trimethoxy silane, triethoxyl silane, methyldiethoxysilane and dimethylethoxysilane.
Generally speaking, if used, linking agent is preferably organopolysiloxane, and for example polydiorganosiloxane for example has formula-Si (R ') 2(OR) polydimethylsiloxane of end unit (this type of end unit that particularly wherein at least one R ' group is alkoxyl group), or each formula-Si (R ') for side chain wherein 2(OR) the branching organopolysiloxane of group end capping.Should be understood that to be box lunch while there is linking agent, still can occur with formula-Si (R ') 2(OR) some of the polyorganosiloxane polyoxyalkylene segmented copolymer interchain of active group end-blocking are cross-linked.Can preferably use a small amount of linking agent to control the performance of cured polymer compositions.For example, can add the branching organopolysiloxane that contains Si-alkoxyl group to improve crosslinked degree and/or density, and then cause harder cured polymer compositions.Can add the alkoxy end-capped polydiorganosiloxane long compared with long-chain (for example DP is 100-250 or 500 polydimethylsiloxane even) to reduce cross-linking density, and then cause having more flexible cured polymer compositions.Polyorganosiloxane polyoxyalkylene copolymers and other overall proportion with the organopolysiloxane of alkoxy-functional with alkoxy-functional can be 100: 0-1: any value of 99.
Si-alkoxyl group divides under existence and reacts each other and form Si-O-Si key at moisture.Even if this reaction does not have catalyzer still can carry out at ambient temperature, but carry out obviously sooner under siloxane condensation catalyst exists.Can use any applicable polycondensation catalyst.These catalyzer comprise protonic acid, Lewis acid, organic and mineral alkali, transistion metal compound, metal-salt and organometallic complex.Siloxane condensation catalyst can for example comprise the compound of the transition metal that is selected from titanium, zirconium and hafnium.Preferred titanium compound is alcohol titanium (being separately called titanic acid ester).Or, can use alcohol zirconium (zirconate) or alcohol hafnium.Catalyzer based on titanic acid ester and/or zirconate can comprise that general formula is respectively Ti[OR 5] 4and Zr[OR 5] 4compound, wherein each R 5can be identical or different, and represent the unit price that can be straight or branched, the primary, secondary or tertiary aliphatic hydrocarbyl that contain 1-10 carbon atom.Optionally, titanic acid ester can contain part unsaturated group.But, R 5preferred embodiment include but not limited to that methyl, ethyl, propyl group, sec.-propyl, butyl, the tertiary butyl and the secondary alkyl of side chain are as 2,4-dimethyl-3-amyl group.Preferably, as each R 5when identical, R 5for sec.-propyl, the secondary alkyl of side chain or tertiary alkyl, the particularly tertiary butyl.Or titanic acid ester can chelating.Can with any applicable sequestrant chelating, for example methyl ethyl diketone acid alkyl ester is as acetopyruvic acid methyl esters or ethyl acetopyruvate.Can use any applicable chelated titanates or zirconate.Preferably; chelation group used is that single ketones ester is as pendant acetoacetonate moieties and alkyl pendant acetoacetonate moieties; and then acquisition chelated titanates, for example two (Acetyl Acetone base) metatitanic acid diisopropyl esters, two (ethylacetoacetone(EAA,HEAA) base) metatitanic acid diisopropyl ester and diisopropoxy titanium two (methyl aceto acetate) etc.The example that is applicable to catalyzer is described in EP1254192 and WO200149774 in addition.
The transistion metal compound existing taking catalyzer as the weight of the amount of titanic acid ester based on polyorganosiloxane polyoxyalkylene copolymers and linking agent can be for example 0.01-2%.
Other the applicable condensation catalyst that can be used as the catalyzer of polyreaction of the present invention comprises the condensation catalyst in conjunction with tin, lead, antimony, iron, cadmium, barium, manganese, zinc, chromium, cobalt, nickel, aluminium, gallium or germanium.Example comprises iron stearate, lead octoate 36, metal salts of trifluoromethane sulphonic acid, organotin metal catalyst, for example tartrate triethyltin, stannous octoate, oleic acid tin, naphthoic acid tin, three-2 ethyl hexanoic acid butyl tin, butyric acid tin, three suberic acid carbomethoxyphenyl tin, three cerinic acid isobutyl-tin (isobutyl tin triceroate), with two organic tin salts, especially be two organotin dicarboxylate compounds, for example dibutyl tin laurate, two butyric acid tin methides, dimethanol dibutyl tin, dibutyltin diacetate, two neodecanoic acid tin methides, dibenzoic acid dibutyl tin, two neodecanoic acid tin methides, acetopyruvic acid dibutyl tin or two sad dibutyl tins.In addition, catalyzer can be organo-bismuth or organophosphate (2-ethylhexyl) esters as two in phosphoric acid hydrogen, or it can comprise halogen organic acid or can form this type of sour derivative in condensation reaction Water Under solution, wherein halogen organic acid is being to have at least one halogenic substituent and/or on the carbon atom that is beta-position with respect to acid groups, have at least one halogenic substituent on the carbon atom put of alpha-position with respect to acid groups.
For example, or catalyzer can be lewis acid catalyst-" Lewis acid " and forms for accepting electron pair any material-boron trifluoride, FeCl of covalent linkage 3, AlCl 3, ZnCl 2, ZnBr 2, formula M 1r 4 fx 1 gcatalyzer, wherein M 1for B, Al, Ga, In or Tl, each R 4independent identical (equally) or different and represent that the unit price aromatic hydrocarbon part with 6-14 carbon atom, this type of unit price aromatic hydrocarbon part preferably have at least one electrophilic element or group as-CF 3,-NO 2or-CN, or replaced by least two halogen atoms; X 1for halogen atom; F is 1,2 or 3; G is 0,1 or 2; Precondition is f+g=3.An example of this type of catalyzer is B (C 6f 5) 3.
The example of alkaline catalysts is that amine or quaternary ammonium compound are as tetramethyl ammonium hydroxide.Amine catalyst can be separately or is combined with as carboxylic acid tin or carboxylic acid organotin with other catalyzer; For example, lauryl amine may be effective especially together with this type of tin compound.
Because the polyorganosiloxane polyoxyalkylene segmented copolymer with Si-alkoxyl group and the linking agent with Si-alkoxyl group do not react under moisture not having, even therefore under catalyzer exists, curable compositions based on it also can be stored in single container, as long as reagent is dry and container is moistureproof.Open after container, curable compositions can be applied to surface upper, it solidifies conventionally under atmospheric moisture exists.Solidify at ambient temperature and carry out rapidly under catalyzer (particularly tetrol titanium or chelating alcohol titanium) exists.A class curable compositions of the present invention comprises the polyorganosiloxane polyoxyalkylene segmented copolymer that contains Si-alkoxyl group, the optional linking agent with Si-alkoxyl group and siloxane condensation catalyst, and wherein said composition is packaged in moisture-proof container.
Although generation can easily be carried out with the hydrosilylation reactions of the polyorganosiloxane polyoxyalkylene segmented copolymer of active Si-H group end capping under factory condition, the system based on this analog copolymer at ambient temperature can fast setting.Therefore, can preferably the polyorganosiloxane polyoxyalkylene copolymers of Si-H end-blocking be converted into the multipolymer with other active group end-blocking.Si-H group can react with the compound that contains ethylenically unsaturated group conventionally, described ethylenically unsaturated group and Si-H group and other active group be as Si-oxyalkylation reaction, and described other active group does not react with Si-H but forms the active group X of resulting polymers.For example, can be for example by with formula Z-Si (R ') 2(OR) the unsaturated organoalkoxysilane of olefinic of (wherein Z is that ethylenically unsaturated group is as vinyl, allyl group, isobutenyl or 5-hexenyl) reacts formula-Si (R ') 2(OR) active group of (wherein R and R ' have implication given above) is introduced and is had in the multipolymer of Si-H functional group.The example of the unsaturated organoalkoxysilane of this type of olefinic is vinyltrimethoxy silane, allyltrimethoxysilanis and methyl ethylene dimethoxy silane.If the polyorganosiloxane polyoxyalkylene segmented copolymer of Si-H end-blocking is formula PS-(A-PO-A-PS) as defined above n, can generate PS '-(A-PO-A-PS ') nthe polyorganosiloxane polyoxyalkylene segmented copolymer of form, wherein PS ' formula-Si for representative (R ') 2(OR) the organopolysiloxane block of the Siliciumatom end-blocking that alkoxyl group replaces, PO represents polyoxyalkylene block, and A represents divalent moiety, and the value of n is at least 1.The polyorganosiloxane polyoxyalkylene segmented copolymer of Si-H end-blocking and the reaction of the unsaturated organoalkoxysilane of olefinic can be used with the organopolysiloxane with regard to Si-H end-blocking above to be carried out with the described identical catalyzer of reacting of olefinic unsaturated polyether and reaction conditions.If used, linking agent also can be prepared by hydrosilylation reactions.For example, can make the organopolysiloxane of Si-H end-blocking react with the unsaturated organoalkoxysilane of olefinic.Or, can make the organopolysiloxane that contains ethylenically unsaturated group react with the polysiloxane that contains Si-H group and at least one Si-alkoxyl group.
With formula Si (R ') (OR) 2the polyorganosiloxane polyoxyalkylene copolymers of active group end-blocking all there is the active alkoxyl group of 2 or 3 Si combinations at each end of copolymer chain.It does not need to react to form network with Gao Guanneng or branching linking agent.The linking agent that class polyorganosiloxane polyoxyalkylene copolymers uses together therewith can be for example for Si-alkoxyl group suc as formula-Si (R ') (OR) 2the polydiorganosiloxane of group end capping as polydimethylsiloxane.This type of alkoxy end-capped polydiorganosiloxane can be by making the polydiorganosiloxane of Si-H end-blocking and formula Z-Si (R ') (OR) 2the reaction preparation under platinum metal catalysts exists of the unsaturated organoalkoxysilane of olefinic.Polydiorganosiloxane can be for example the polydimethylsiloxane of 4-500 siloxane unit for DP.For using formula-Si (R ') (OR) 2the linking agent of polyorganosiloxane polyoxyalkylene copolymers of active group end-blocking can or or comprise in addition contain-Si (R ') 2(OR) the branching organopolysiloxane of group, wherein R and R ' are as defined above.Branching organopolysiloxane can be for example Q branched polysiloxane, wherein all use-Si of each side chain (R ') 2(OR) group end capping.This type of branching organopolysiloxane can for example, by making the unsaturated branching organopolysiloxane of olefinic (the above-mentioned Q branched silicone with vinyl-functional) and containing Si-H group and formula-Si (R ') 2(OR) reaction under platinum metal catalysts exists of the short chain polysiloxane (polysiloxane of for example following formula) of group forms.
Or branching organopolysiloxane linking agent can be for example, by the branching organopolysiloxane that contains Si-H group (having the Q branched polysiloxane of end dimethyl hydrogen silyl) and formula Z-Si (R ') (OR) 2the preparation of the unsaturated organoalkoxysilane of olefinic.Can preferably use the mixture of alkoxy end-capped polydiorganosiloxane and alkoxy end-capped Q branched polysiloxane.
Other composition
Also can comprise one or more vehicle and/or filler, one or more pigment or dyestuff, dehumidizier and unreactive fluid for coating composition of the present invention.The example that is applicable to vehicle or filler is barium sulfate, calcium sulfate, calcium carbonate, silica or silicate (for example talcum, feldspar and china clay), comprise fumed silica, wilkinite and other clay and be generally the solid polyorganosiloxane resin of the branched polysiloxane of condensation, for example, contain formula SiO 4/2q unit and formula R m 3siO 1/2the polyorganosiloxane resin of M unit, wherein R msubstituting group is selected from the alkyl with 1-6 carbon atom, and M unit is 0.4 with the ratio of Q unit: 1-1: 1.The example of pigment comprises that Black Rouge, titanium dioxide, Metal Flake material (for example aluminium flake) or other so-called obstruct pigment or anticorrosive pigment are as zinc powder or zinc alloy.Pigment volume concentration (PVC) is preferably 0.5-25%.
Applicable unreactive fluid is silicone oil as methyl phenyl silicone oil, oil, polyolefin oil, poly-aromatic substance oil, fluoro-resin is as tetrafluoroethylene or contain fluoro-alkyl or the liquid polymer of alkoxyl group or its combination.Preferred unreactive fluid is methyl phenyl silicone oil.The solids content of the ratio coating based composition of reacting fluid is not preferably 5-25 % by weight, more preferably 5-10 % by weight.
The solids content (being defined as the weight percentage of nonvolatile substances) of coating composition is preferably 35 % by weight, more preferably at least 50 % by weight, even more preferably at least 70 % by weight.Solids content can be 100 % by weight at the most, preferably 95 % by weight at the most, more preferably 90 % by weight at the most, most preferably 80 % by weight at the most.
Coating
Allow to form substantially water insoluble and there is the solidified coating of hydrophilicity according to coating composition according to the present invention.
When dry, coat-thickness is preferably 50-400 micron, and more preferably 75-250 micron, most preferably is 100-200 micron.
Described coating is particularly suited for preventing from being subject to underwater structures with physics mode and spatters aquatic organism on belt surface as the pollution of algae, barnacle and mussel with wave under water as the cooling water inlet in hull, power station, fish-culture equipment and production vessel.
Embodiment
Embodiment 1
In three-necked flask, the polyoxyethylene glycol diallyl ether that is 10 by average 37.5g DP is placed in 31.20g toluene, and in nitrogen, be heated to 65 DEG C, drip successively subsequently the polydimethylsiloxane fluid of the dimethyl hydrogen silyl end-blocking that 165 μ l chloroplatinic acid catalysts and the average DP of 100g are 6.7.Si:H group and allylic mol ratio are 3: 1.Mixture is heated 1 hour at 80 DEG C, cooling to form the polysiloxane polyoxyethylene block copolymer solution of the Si-H content Si-H end-blocking as 5.36% subsequently.
The polymers soln of preparation is above mixed to the Si:H group of polysiloxane polyoxyethylene block copolymer of the acquisition Si-H end-blocking of 1.4: 1 and the mol ratio of vinyl with the Q branched polysiloxane that is dissolved in the platinum vinyl siloxane complex of 2 % by weight in vinyl siloxane copolymer with 0.5% platinum and has altogether a following formula ethenyl blocking of 100 siloxanes D unit.
Mixture is applied in test plate surface, and leaves standstill 1 hour at ambient temperature.Composition is cured as water-fast coating.
Embodiment 2
Repeat embodiment 1, wherein with same general formula but contain altogether the Q branched polysiloxane replacement Q branching linking agent of 225 siloxanes D unit, and make the mol ratio of Si-H and vinyl remain on 1.4: 1.Mixture is applied in test plate surface, and leaves standstill 1 hour at ambient temperature.Gained coating is softer than the coating obtaining in embodiment 1.
Embodiment 3
Repeat embodiment 1, wherein with same general formula but contain altogether the Q branched polysiloxane replacement Q branching linking agent of 4 siloxanes D unit, and make the mol ratio of Si-H and vinyl remain on 1.4: 1.Mixture is applied in test plate surface, and leaves standstill 1 hour at ambient temperature.Gained coating is harder and crisp than the curing composition of embodiment 1.
Embodiment 4 and 5
By the polysiloxane polyoxyethylene block copolymer of the Si-H end-blocking of preparation in embodiment 1 with etc. the polydimethylsiloxane mixing of the identical in fact Si-H end-blocking of the Si-H content of weight.By this mixture be dissolved in the platinum vinyl siloxane complex of 2 % by weight in vinyl siloxane copolymer and the Q branched polysiloxane of ethenyl blocking with 0.5% platinum and mix the ratio that obtains the Si-H of 1.4: 1 and vinyl.Q branched polysiloxane contains 100 siloxanes D unit (embodiment 4) or 225 siloxanes D unit (embodiment 5).As described in Example 1 resulting composition be applied on test surfaces and solidify.Make water-fast coating.
Embodiment 6-8
The polydimethylsiloxane of Si-H end-blocking identical in fact with Si-H content the polysiloxane polyoxyethylene block copolymer of the Si-H end-blocking of preparation in embodiment 1 is mixed with the weight ratio of 50: 50 (embodiment 6), 30: 70 (embodiment 7) and 10: 90 (embodiment 8).Every kind of these mixture is mixed with the Q branched polysiloxane that is dissolved in the platinum vinyl siloxane complex of 2 % by weight in vinyl siloxane copolymer and the ethenyl blocking of embodiment 3 with 0.5% platinum and obtain the Si-H of 1.4: 1 and the ratio of vinyl.As described in Example 1 resulting composition be applied on test surfaces and solidify.Make water-fast hydrophilic coating.
Embodiment 9-11
Prepare as described in example 1 above the polysiloxane polyoxyethylene block copolymer of Si-H end-blocking, but the polydimethylsiloxane fluid of the dimethyl dihydro silyl end-blocking that is wherein 19 with average DP replaces polydimethylsiloxane fluid, the polyoxyethylene glycol diallyl ether that is 4.5 with the average DP of 6.20g replaces polyoxyethylene glycol diallyl ether (Si-H: allylic ratio is 3: 1).The Si-H content of the polysiloxane polyoxyethylene block copolymer making is 2.85%.In embodiment 9-11, the Q branched polysiloxane that this polysiloxane polyoxyethylene block copolymer is passed through respectively the ethenyl blocking of embodiment 1,2 and 3 solidifies.The polysiloxane of ethenyl blocking is for obtaining the amount of 1.2 (embodiment 9 and 10) or 1.4 Si-H of (embodiment 11) and the ratio of vinyl.In each embodiment, all make water-fast hydrophilic coating.Generally speaking, described coating is slightly harder than the corresponding coating of embodiment 1-3.
Embodiment 12-14
The polydimethylsiloxane of Si-H end-blocking identical in fact with Si-H content the polysiloxane polyoxyethylene block copolymer of the Si-H end-blocking of preparation in embodiment 9 is mixed with the weight ratio of 50: 50 (embodiment 12), 30: 70 (embodiment 13) and 10: 90 (embodiment 14).Every kind of this type of mixture is obtained to the Si-H of 1.4: 1 ratio to vinyl with being dissolved in the platinum vinyl siloxane complex of 2 % by weight in vinylsiloxane polymkeric substance with 0.5% platinum and mixing with the Q branched polysiloxane of the ethenyl blocking of embodiment 3.As described in example 1 above resulting composition be applied on test surfaces and solidify.Make water-fast hydrophilic coating.
Embodiment 15
Prepare as described in example 9 above the polysiloxane polyoxyethylene block copolymer of Si-H end-blocking.The Si-H content of described segmented copolymer is 2.42% and comprises residual catalyst.In three-necked flask, the polysiloxane polyoxyethylene block copolymer of 100gSi-H end-blocking is placed in to 30g toluene, and in nitrogen, is heated to 65 DEG C.Drip 37.16g vinyltrimethoxy silane.The mol ratio of Si:H group and vinyl is 1: 3.This mixture is heated 1 hour at 80 DEG C, cooling to form (the CH with Si subsequently 3) 2-CH 2cH 2-Si (OCH 3) 3the polysiloxane polyoxyethylene block copolymer solution of group end capping.The number-average molecular weight Mn of described multipolymer is 3,535 and the methoxyl group that contains 6.95 % by weight.Be extremely the degree of 0.1 % by weight Ti based on multipolymer by the multipolymer of the Si-methoxyl group end-blocking of embodiment 15 and four n-butyl titanium catalyst mix, be applied on test surfaces, and allow in humid atmosphere, to solidify at ambient temperature.Make hydrophilic coating.
Embodiment 16
The Q branched polysiloxane of ethenyl blocking of embodiment 3 and the polydimethylsiloxane with trimethoxysilyl functional group of the Si-H end-blocking that the DP of following form is 4 are reacted in the presence of the platinum vinyl siloxane complex that is dissolved in 2 % by weight in vinyl siloxane copolymer with 0.5% platinum, taking preparation Mn as 1,657 and methoxy content be the linking agent with Si-methoxy functional group of the branching of 25.55 % by weight.
Be extremely the degree of 0.1 % by weight Ti based on total siloxanes by the multipolymer (9.09g) of the Si-methoxyl group end-blocking of embodiment 15 with branching linking agent and the blending of four n-butyl titanium catalyzer of 0.91g Si-methoxyl group end-blocking, mixture is applied on test surfaces, and allows in humid atmosphere, to solidify at ambient temperature.Make hydrophilic coating.
Embodiment 17-19
Repeat embodiment 16, just replace the multipolymer of the Si-methoxyl group end-blocking of embodiment 15 with the polydimethylsiloxane of Si-methoxyl group end-blocking with the weight ratio part of 50: 50 (embodiment 17), 30: 70 (embodiment 18) and 10: 90 (embodiment 19).Described Si (CH for polydimethylsiloxane 3) 2-CH 2cH 2-Si (OCH 3) 3group end capping, and there is molecular weight and the methoxy content close with the multipolymer of embodiment 15.Each composition is cured as to hydrophilic coating.
Embodiment 20
After embodiment 15 programs, make in 100g embodiment 1 the polysiloxane polyoxyethylene block copolymer of the Si-H end-blocking of preparation react with 85.46g vinyltrimethoxy silane (Si-H is 1: 3 with the ratio of vinyl) taking prepare Mn as 1,754, use Si (CH 3) 2-CH 2cH 2-Si (OCH 3) 3group end capping and methoxy content are the polysiloxane polyoxyethylene block copolymer of 18.47 % by weight.By the degree of the multipolymer of the Si-methoxyl group end-blocking of embodiment 20 and four n-butyl titanium catalyst mix to 0.1 % by weight Ti, be applied on test surfaces, and allow in humid atmosphere, to solidify at ambient temperature.Make hydrophilic coating.
Embodiment 21
The multipolymer (9.03g) of the Si-methoxyl group end-blocking of embodiment 20 and branching linking agent and the four n-butyl titanium catalyzer of the Si-methoxyl group end-blocking described in 0.97g embodiment 16 are admixed to the degree to 0.1 % by weight Ti, mixture is applied on test surfaces, and allows in humid atmosphere, to solidify at ambient temperature.Make hydrophilic coating.
Embodiment 22-24
Repeat embodiment 21, just replace the multipolymer of the Si-methoxyl group end-blocking of embodiment 20 with the polydimethylsiloxane of Si-methoxyl group end-blocking with the weight ratio part of 50: 50 (embodiment 22), 30: 70 (embodiment 23) and 10: 90 (embodiment 24).Described Si (CH for polydimethylsiloxane 3) 2-CH 2cH 2-Si (OCH 3) 3group end capping, and there is molecular weight and the methoxy content close with the multipolymer of embodiment 20.By the degree of each adulterant and four n-butyl titanium catalyst mix to 0.1 % by weight Ti, be applied on test surfaces, and allow in humid atmosphere, to solidify at ambient temperature.Each composition is cured as to hydrophilic coating.
Embodiment 25
In three-necked flask, the polydimethylsiloxane fluid of the dimethyl hydrogen silyl end-blocking that is 11.8 by average 100g DP is placed in 50g toluene, and in nitrogen, is heated to 80 DEG C.Add the polyoxyethylene glycol diallyl ether that 1 average DP is 7, drip successively subsequently 30 μ l chloroplatinic acid catalysts and 12.76g polyoxyethylene glycol diallyl ether.Si:H group and allylic mol ratio are 3: 1.Mixture is heated 1 hour at 80 DEG C, cooling to form the polysiloxane polyoxyethylene block copolymer solution of the Si-H content Si-H end-blocking as 3.10% subsequently.
In three-necked flask, the polysiloxane polyoxyethylene block copolymer of Si-H end-blocking described in 100g is placed in to 50g toluene, and in nitrogen, is heated to 80 DEG C.Add 30 μ l chloroplatinic acid catalysts, drip subsequently 54.75g vinyltrimethoxy silane.The mol ratio of Si:H group and vinyl is 1: 3.Mixture is heated 1 hour at 80 DEG C, cooling to form (the CH with Si subsequently 3) 2-CH 2cH 2-Si (OCH 3) 3the polysiloxane polyoxyethylene block copolymer solution of group end capping.The number-average molecular weight Mn of described multipolymer is 2,611, and the methoxyl group that contains 10.26 % by weight.Be extremely the degree of 0.1 % by weight Ti based on multipolymer by the multipolymer of the Si-methoxyl group end-blocking of embodiment 25 and four n-butyl titanium catalyst mix, be applied on test surfaces, and allow in humid atmosphere, to solidify at ambient temperature.Make hydrophilic polymer coating.
Embodiment 26: antifouling test
By brush the coating composition of embodiment 11-14 is applied to (to build for～300 μ m) sea of 60cm × 60cm with on plywood panel, epoxy primer and two kinds of coating bottoming of acrylic acid series tack coat for described panel.Apply six samples of each coating composition.Application standard antifouling coating and nontoxic contrast are as the Quantityanddiversity with reference to for coating assessment relative performance of the present invention and pollution sedimentation.
By test panel from being designed for the raft submergence on submergence experiment test surface, the representative of conditions that condition experiences for the hull of pleasure-boat or ship.Panel is fixed on testing jig, and is hung vertically in 0.5-1.5m below the water surface in each test point.Make regular check on panel with regard to biological pollution existence and coating integrity.Test point comprises: Changi, and Singapore and Newton Ferrers, UK, it has the typical case's pollution that comes from all main contamination classs.Contamination class with four kinds of main ecology sources is evaluated polluting fraction of coverage: microbial contamination, weeds, software animal and hardware animal, and analyze for these four kinds of contamination class range estimations, because this provides the enough information of distinguishing coating performance, also allow to carry out some general comparisons between test point simultaneously.The results are shown in following table.Data in this table relate to the gross contamination fraction of coverage (being expressed as a percentage) on test panel surface.
Table
Changi, Singapore, 17 weeks Newton Ferrers, UK, 26 weeks
Embodiment 11 64.0 5.3
Embodiment 12 45.0 3.0
Embodiment 13 34.0 15.0
Embodiment 14 58.0 26.3
Standard antifouling coating 83.0 20.0
Only anticorrosive bottom 93.0 95.0
This table shows in Singapore waters submergence after 4 months and in UK submergence after 6 months, the pollution of gathering is obviously less than the pollution of the control substrates that only scribbles anti-corrosive primer, and is less than the pollution of standard substrate.Any pollution in the coating of embodiment 11-14 all can be by rubbing and remove easily lightly, and the pollution of gathering in control substrates can not be removed in a similar manner.

Claims (16)

1. one kind prevents substrate contaminated method in aquatic contaminate environment with physics mode, described method forms coating composition before being included in and being exposed to described environment on substrate, described coating composition comprises (i) and has at least two curable polyorganosiloxane polyoxyalkylene segmented copolymers that are positioned at the active group X on copolymer chain, and wherein polyorganosiloxane polyoxyalkylene segmented copolymer is PS-(A-PO-A-PS) nthe segmented copolymer of form, wherein PS represents organopolysiloxane block, and PO represents polyoxyalkylene block, and A represents divalent moiety, the value of n is 10-250, and (ii) has organosilicon cross-linking agent and/or the catalyzer of at least two active group Y that react with described active group X.
2. according to the process of claim 1 wherein that described active group X reacts each other, wherein coating composition comprise catalyzer and optional described in there is the organosilicon cross-linking agent of at least two active group Y that react with described active group X.
3. according to the process of claim 1 wherein that described active group X does not react each other, wherein coating composition comprises the organosilicon cross-linking agent with at least two active group Y that react with described active group X.
4. according to the method for claim 3, wherein the each molecule of polyorganosiloxane polyoxyalkylene segmented copolymer has two active group X on organopolysiloxane block, and the each molecule of wherein said organosilicon cross-linking agent on average has plural active group Y.
5. according to the method for claim 3 or 4, wherein active group X is Si-H group, and described organosilicon cross-linking agent contains ethylenically unsaturated group as active group Y.
6. according to the method for claim 5, wherein coating composition comprises the catalyzer that contains platinum metals, and be packaged in two containers, thereby make polyorganosiloxane polyoxyalkylene segmented copolymer, described organosilicon cross-linking agent and catalyzer not all in same package.
7. according to the method for claim 2, wherein active group X is the Si-alkoxyl group reacting each other, and if have described organosilicon cross-linking agent, active group Y is also Si-alkoxyl group.
8. according to the method for claim 7, wherein active group X is formula-Si (R ') 2(OR) structure, wherein R representative has the alkyl of 1-4 carbon atom, and each R ' representative has the alkoxyl group of alkyl, phenyl or the formula-OR of 1-6 carbon atom.
9. according to the method for claim 7, wherein composition comprises siloxane condensation catalyst, and composition is packaged in moisture-proof container.
10. method according to Claim 8, wherein composition comprises siloxane condensation catalyst, and composition is packaged in moisture-proof container.
11. according to the method for any one in claim 7-10, and wherein each organopolysiloxane block is polydimethylsiloxaneblock block.
12. according to the method for claim 2, and wherein active group X is the Si-alkoxyl group reacting each other, and if have described organosilicon cross-linking agent, active group Y is silanol group.
13. according to the method for claim 2, and wherein active group X is the silanol group reacting each other, and if have described organosilicon cross-linking agent, active group Y is selected from alkoxyl group, acetoxyl group, ketoxime base, amide group or the hydroxyl of being combined with silicon.
14. according to the process of claim 1 wherein in polyoxyalkylene block that at least 50% polyoxyalkylene unit is oxygen ethylene unit.
15. 1 kinds are coated with cated substrate, obtain by the following method described coating:
A) application of paint composition from the teeth outwards, described coating composition comprises (i) and has at least two curable polyorganosiloxane polyoxyalkylene segmented copolymers that are positioned at the active group X on multipolymer, and wherein polyorganosiloxane polyoxyalkylene segmented copolymer is PS-(A-PO-A-PS) nthe segmented copolymer of form, wherein PS represents organopolysiloxane block, PO represents polyoxyalkylene block, A represents divalent moiety, the value of n is 10-250, and (ii) has organosilicon cross-linking agent and/or the catalyzer of at least two active group Y that react with described active group X, and
B) with coating composition described in after fixing.
16. according to the substrate of claim 15, and wherein substrate is underwater structures.
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